Fertilizer compositions containing tetraisopropylnaphthalene

ABSTRACT

This invention relates to novel compositions having improved resistance to liquid water. Specifically the invention relates to slow release fertilizer compositions containing one or more isomers of tetraisopropylnaphthalene.

United States Patent Inventors Seymour W. Ferris, deceased late of Vincentown, N.J. by Lucretia G.

Ferris, executrix; Ernest P. Black, West Chester; Andrew J. Bozzelll, Springfield, Pa.

Appl. No. 685,712

Filed Nov. 24, 1967 Patented Nov. 2, 1971 Assignee Sun Oil Company P. O. Box 426, Marcus Look, Pa. 19061 FERTILIZER COMPOSITIONS CONTAINING TETRAISOPROPYLNAPI-ITIIALENE 18 Claims, No Drawings U.S. Cl. 71/28,

[51] Int. Cl....' C05c 9/00 [50] Field of Search 7 l /28, 64

[56] References Cited UNITED STATES PATENTS 3,205,061 9/1965 Mason 71/64 X Primary Examiner-J. L. DeCesare Anomey-Donald R. Johnson ABSTRACT: This invention relates to novel compositions having improved resistance to liquid water. Specifically the invention relates to slow release fertilizer compositions containing one or more isomers of tetraisopropyInaphthalene.

FERTILIZER COMPOSITIONS CONTAINING TETRAISOPROPYLNAPHTIIALENE This invention relates to novel compositions having improved resistance to liquid water and other aqueous fluids and to methods of their preparation. The compositions of the invention contain urea or an adduct of urea and paraffin wax as the active fertilizer ingredient. In addition to the active fertilizer ingredient, the compositions of the present invention contain tetraisopropylnaphthalene which has been found to provide improved water resistance.

Nitrogen, potassium, and phosphorus are essential elements for plant growth. Commercially available fertilizers contain one or more of these elements. Examples of the fertilizers in frequent use at the present time include urea, ammonium nitrate, potassium chloride, sodium nitrate, monoammonium phosphate, diammonium phosphate, potassium sulfate, calcium cyanamide, potassium phosphate, potassium nitrate, superphosphate (a mixture of calcium acid phosphate and calcium sulfate), and triple superphosphate (calcium acid phosphate). Urea is a preferred fertilizer because it contains a higher percentage of nitrogen than the other nitrogen compounds mentioned.

The number of fertilizer compounds applied to the soil at a t given time depends mainly upon the soil analysis and the crops to be grown. In some cases only nitrogen is needed; hence only a nitrogen fertilizer is applied. In the majority of cases, however, all three of the essential elements are needed and in such cases the fertilizer actually applied to the soil is a blend of a nitrogen fertilizer, a potassium fertilizer, and a phosphorus fertilizer. Some compounds such as diammonium phosphate contain more than one essential element. A fertilizer containing all three essential elements is conventionally referred to as a complete fertilizer. Most conventional fertilizers, whether complete or otherwise, contain some inert material added to maintain the percentage of the essential elements present in the fertilizer at a relatively low level in an attempt to avoid excessive local concentrations of, say, nitrogen in the soil which may result in burned" crops.

Unfortunately most of the commercial fertilizers mentioned above are readily water soluble, thus creating a number of disadvantages. In a heavy rainfallmuch of the fertilizer may be dissolved in the rainwater and soaked into the ground below the plant roots or rapidly transported away by flowing surface water. This fertilizer never becomes available to the plants. Another disadvantage is that the fertilizer often becomes available to the plant too rapidly resulting in injury to the plant rather than benefit. This is often noticed in "burned" lawns or crops.

One method of reducing the rate at which the fertilizer, e.g., urea, is consumed or washed away is to disperse it in a wax composition. The urea is dispersed in molten wax and the resulting slurry is formed into small particles in a mold. The particles are then allowed to cool. The resulting composition is a dispersion of solid urea particles in solid wax useful as a slow release fertilizer.

In areas of heavy rainfall the wax content of a slow release fertilizer is relatively high in order to provide a satisfactory reduction in the rate at which the fertilizer is released to'the plants. The relatively high proportion of wax may make the fertilizer too expensive for commercial acceptance. Fertilizer compositions containing a relatively low amount of wax and yet having a high resistance to leaching by water are desirable. A means of improving the water resistance of the urea-wax fertilizer is also desirable.

It has now been discovered that the water-resistance of waxurea compositions can be improved by replacing some or all of the wax with tetraisopropylnaphthalene (TIPN). Although all of the wax can be replaced by TIPN, preferably only a minor amount, most preferably 1 to 20 percent by weight of the wax, is so replaced. If only a minor amount of the wax is being replaced with TIPN, any particular isomer thereof can be used but preferably the l,3,5,7-isomer is employed. Most preferably the TlPN used is a mixture containing 80 to 99 percent by weight of the l,3,5,7-isomer and l to 20 percent of the l,3,6,7-isomer. This mixture can be prepared by the alkylation of naphthalene with propylene in the presence of hydrogen fluoride. This reaction will give about 90 to 99 weight percent l,3,5,7-tetraisopropylnaphthalene, l to 10' weight percent l,3,6,7-tetraisopropylnaphthalene and small amounts of mixed tri-isopropylnaphthalenes and pentaisopropylnaphthalenes.

If all or more than a minor amount of the wax is to be substituted, the compound substituting a wax must have a melting point high enough so that the melting point of the coating phase of the resulting fertilizer will be used. For example, the

l,3,6,7-isomer of TIPN melts at about 93 C. and is suitable as the sole coating material for urea. Similarly, a mixture of wax and this isomer containing a major amount of the latter is suitable as the coating phase of a slow release fertilizer composition. Also the l,3,5,7-isomer which melts at about I29 C. is suitable. The l,3,5,7-l,3,6,7-isomer mixture described above is also suitable.

Other methods than that described abovecan be employed to produce tetraisopropylnaphthalenes useful in the present invention. U.S. Pat. No. 3,129,255 teaches thealkylation of naphthalene with propylene in the presence of an ethyl aluminum sesquichloridetitanium tetrachloride catalyst to give a product comprising about 50 weight percent l,3,5,7- tetraisopropylnaphthalene. Chemical Abstracts, Volume 50, columns 9353f to 9354b, teaches reacting isopropylchloride and naphthalene with aged 2 to give nearly 100 percent tetraisopropylnaphthalene, and Chemical Abstracts, Volume 49, column 13 l92b to 0, discusses the same reaction in more detail.

The present invention is directed to wax compositions which exhibit improved water resistant characteristics and which contain tetraisopropylnaphthalenes. The invention also relates to slow release fertilizer compositions containing tetraisopropylnaphthalene. The compositions can comprise urea or an adduct of urea and paraffin wax as the fertilizer ingredient combined with wax and tetraisopropylnaphthalene or tetraisopropylnaphthalene alone as the release agent. The improvement of the present invention resides in the presence of the tetraisopropylnaphthalene. The compositions to which this component can be added to impart improved water-resistant characteristics are numerous. For example, U.S. Pat. No. 3,300,293 teaches fertilizer compositions comprising a dispersion of'a urea-paraffin wax adduct in petroleum wax. These compositions can contain asphalt. They are prepared by reacting solid urea with molten paraffin wax until a ureaparaffin wax adduct is obtained. The reaction product is then cooled to a temperature below the melting point of said paraffin wax to give a dispersion of urea-paraffin wax adduct in solid wax.

U.S. Pat. No. 3,252,786 discloses slow release fertilizer compositions comprising a dispersion of solid urea in wax. The wax additionally. contains a minor amount of a particular wood rosin. These compositions are prepared by heating paraffin wax to above its melting point, dissolving the wood rosin in the wax'as an adduct inhibitor, dispersing solid urea in the molten wax and cooling the resulting dispersion.

The present invention comprises the compositions of these patentswiththe improvement that all or a portion of the petroleum wax in these compositions has been replacedwith tetraisopropylnaphthalene. ln this specification the term tetraisopropylnaphthalene" means any of the known isomers of tetraisopropylnaphthalene as individual components or comprising a urea-paraffin wax adduct in wax, the amount of adduct is in the range of five to 99 parts, preferably to 90 parts and the amount of tetraisopropylnaphthalene and wax, if any, is in the range of one to 40 parts, preferably 10 to 40. 1f asphalt is added to this composition, it is added in an amount to give 5 to 40 percent based on the total composition weight.

U.S. Pat. No. 3,204,061 teaches that in the preparation of slow release fertilizers, the adduction of urea and molten paraffin wax can be prevented or at least substantially delayed by incorporating a small amount of certain polyalkylaromatic hydrocarbons into the wax. The polyalkylaromatic hydrocarbons suitable in the process and compositions of this patent are defined as aromatic hydrocarbons having at least two alkyl groups attached to nuclear carbon atoms of one aromatic nucleus, the alkyl groups containing at least 5 carbon atoms. This teaching is in contrast to the present invention wherein a particular aromatic hydrocarbon having four alkyl groups of 3 carbon atoms attached to nuclear carbon atoms is incorporated into fertilizer compositions to surprisingly give compositions of improved water resistance.

The following examples specifically illustrate the present invention:

Examples 1 and 11 illustrate preparations of tetraisopropylnaphthalene compositions useful in the present invention.

EXAMPLE! One mole (128 g.) of naphthalene and 45 moles of anhydrous hydrogen fluoride were charged into a 1 l. stirred Parr autoclave equipped with an internal cooling coil. Propylene was added with stirring at a rate of 1.0 to 1.5 mole per hour through a calibrated flowmeter at an initial pressure of 15 to 30 p.s.i.g. and the reactor temperature was maintained at ca. C. The addition of propylene was continued over a period of 8 hours. Toward the end of the reaction the propylene flow had decreased to a fraction of the initial rate while the reactor pressure increased to 100 p.s.i.g.

The reaction mixture was quenched in ice-water and extracted with pentane. The organic layer was extracted with dilute sodium hydroxide solution then with water an dried acetone prior to the recrystallization from pentane. The purified solid melted at 1 17 to 124 and analyzed as follows:

Tetra-isopropylnaphthalene wt i 1357- 91.2 I,3,6,7- 5.2

Tri-isopropylnaphthalcne um) 10 Penta-isopropylnaphthdlene (x,x,x,x,x-)

The purified samples from examples 1 and 11 exhibited cooling plateaus at 1 19 C. and 117 C. respectively.

EXAMPLES 111 AND W The following comparative examples illustrate the improved water resistance of wax compositions containing tetraisopropylnaphthalene. Two compositions were prepared. The first composition contained 60 percent urea and percent coating. The coating was 90 percent paraffin wax, 5 percent asphalt and 5 percent rosin. When submerged in water for 500 hours, 40 percent of the urea was dissolved in the water. The second composition was the same except that all the paraffin wax was replaced by a mixture containing 90 percent of the same type paraffin wax and 10 percent tetraisopropylnaphthalene. The tetraisopropylnaphthalene contained 95.5 percent of 1,3,5,7-isomer, 1.5 percent of the l,3,6,7-isomer and 3 percent impurities. When this composition was submerged in water for 500 hours only 10 percent of the urea was leached out. Thus the inclusion of the tetraisopropylnaphthalene in the composition substantially improved the water resistance of the composition.

EXAMPLES V TO XIV Table I gives examples of various compositions of the present invention. All of these compositions contain tetraisopropylnaphthalene and all exhibit improved water resistance compared to similar compositions which do not contain tetraisopropylnaphthalene.

TABLE I Weight percent Component 1,3,5,7-tetraisopropylnaphthalene. 1,3,6,T-tetraisopropylnaphthalen Petroleum wax Polymerized wood rosin (oxidized).. Hydrogenated wood rosin (oxidized) Alcohol esters of wood rosin (oxidized) Wood rosin metal salts (oxidized) Urea-paraflin wax adduet Urea Analysis of the purified sample Tclra-isopropylnuphthalene wt 5 1.3.5.7- 95.5 l,3,6,7- 1.5

EXAMPLE 1] Essentially the same reaction conditions and quantities of the reactants were used as in example 1; however, the procedure included an additional recrystallization from We claim:

1. A slow release fertilizer of improved resistance to water comprising a dispersion of solid urea in a solid petroleum wax composition comprising a major amount of petroleum wax and a minor amount of tetraisopropylnaphthalene, said fertilizer being characterized in that substantially all the particles of said solid urea are surrounded by and encased in said petroleum wax composition.

2. A slow release fertilizer of improved resistance to water comprising a dispersion of solid urea in a solid wax composition comprising a major amount of petroleum wax, a minor amount of tetraisopropylnaphthalene and a minor amount of wood rosin selected from the group consisting of l) polymerized wood rosin, (2) hydrogenated wood rosin, (3) mono and polyhydric alcohol esters of wood rosin, polymerized wood rosin and hydrogenated wood rosin, and (4) polyvalent metal salts of wood rosin, polymerized wood rosin, and hydrogenated wood rosin, each of l (2), 3) and (4) being partially oxidized to an extent equivalent to oxidation at F. in the presence of air at atmospheric pressure under substantially static conditions, for a period of l to 8 composition, said partial oxidation being sufficient to increase the resistance to liquid water of said composition, said fertilizer being characterized in that substantially all the particles of said solid urea are surrounded by and encased in said solid wax composition.

3.'A composition according to claim 2 wherein said rosin is polymerized wood rosin.

4. Composition according to claim 2 wherein said rosin is the calcium salt of polymerized wood rosin containing, before said partial oxidation, 7 to percent calcium.

5. Composition according to claim 4 having a minor amount of asphalt dissolved therein.

6. Composition according to claim 2 wherein the amount of urea is five to 80 parts, the total amount of wax, tetraisopropylnaphthalene and rosin is l5 to 49 parts, and the amount of rosin is 2 to percent based on the total weight of wax, tetraisopropylnaphthalene and rosin.

7. A particulate slow release fertilizer composition which comprises a dispersion of a urea-paraffin wax adduct in a petroleum wax composition comprising a major amount of petroleum wax and a minor amount of tetraisopropylnaphthalene.

8. Composition according to claim 7 wherein the amount of adduct is in the range of five to 99 parts and the amount of the wax-tetraisopropylnaphthalene composition is in the range of one to 40 parts.

9. Composition according to claim 7 wherein the waxtetraisopropylnaphthalene composition contains 5 to 40 percent of asphalt, based on the total weight.

10. Composition according to claim 9 wherein the amount of adduct is in the range of 10 to 90 parts and the amount of the wax-tetraisopropylnaphthalene is in the range of ID to 40 parts.

11. A slow release fertilizer of improved resistance to water comprising a dispersion of solid urea in tetraisopropylnaphthalene, said fertilizer being characterized in that substantially all the particles of said solid urea are surrounded by and encased in tetraisopropylnaphthalene.

12. A slow release fertilizer of improved resistance to water comprising a dispersion of solid urea in a solid composition comprising a major amount of tetraisopropylnaphthalene and a minor amount of wood rosin selected from the group consisting of l polymerized wood rosin, (2) hydrogenated wood rosin, (3) mono and polyhydric alcohol esters of polymerized, hydrogenated, and unmodified wood rosin, a'nifl i") pol vsrem' metal salts of polymerized, hydrogenated, and unmodified wood rosin, each of l (2), (3), and (4) being partially oxidized to an extent equivalent to oxidation at 140 F. for a period of l to 8 days, said partial oxidation being sufficient to result in a decreased rate of leaching when said composition is contacted with water said fertilizer being characterized in that substantially all the particles of said solid urea are surrounded by and encased in said solid composition.

13. Composition according to claim 12 wherein the amount of urea is five to parts, the total amount of tetraisopropylnaphthalene and rosin is 15 to 49 parts, and the amount of rosin is 2 to 20 percent based on the total weight of tetraisopropylnaphthalene and rosin.

l4. Composition according to claim 12 having a minor amount of asphalt dissolved therein.

15. A particulate slow release fertilizer composition which comprises a dispersion of a urea-paraffin wax adduct in tetraisopropylnaphthalene.

l6. Composition according to claim 15 wherein the amount of adduct is in the range of five to 99 parts and the amount of the tetraisopropylnaphthalene is in the range of one to 40 arts.

p 17. Composition according to claim 15 wherein the tetraisopropylnaphthalene contains 5 to 40 percent asphalt based on the total weight of the asphalt and tetraisopropylnaphthalene.

l8. Composition according to claim 17 wherein the amount of adduct is in the range of 10 to parts and the amount of the tetraisopropylnaphthalene and asphalt is in the range of 10 to 40 parts. 

2. A slow release fertilizer of improved resistance to water comprising a dispersion of solid urea in a solid wax composition comprising a major amount of petroleum wax, a minor amount of tetraisopropylnaphthalene and a minor amount of wood rosin selected from the group consisting of (1) polymerized wood rosin, (2) hydrogenated wood rosin, (3) mono and polyhydric alcohol esters of wood rosin, polymerized wood rosin and hydrogenated wood rosin, and (4) polyvalent metal salts of wood rosin, polymerized wood rosin, and hydrogenated wood rosin, each of (1), (2), 3) and (4) being partially oxidized to an extent equivalent to oxidation at 140* F. in the presence of air at atmospheric pressure under substantially static conditions, for a period of 1 to 8 Days, the amounts being based on the total weight of the whole composition, said partial oxidation being sufficient to increase the resistance to liquid water of said composition, said fertilizer being characterized in that substantially all the particles of said solid urea are surrounded by and encased in said solid wax composition.
 3. A composition according to claim 2 wherein said rosin is polymerized wood rosin.
 4. Composition according to claim 2 wherein said rosin is the calcium salt of polymerized wood rosin containing, before said partial oxidation, 7 to 10 percent calcium.
 5. Composition according to claim 4 having a minor amount of asphalt dissolved therein.
 6. Composition according to claim 2 wherein the amount of urea is five to 80 parts, the total amount of wax, tetraisopropylnaphthalene and rosin is 15 to 49 parts, and the amount of rosin is 2 to 20 percent based on the total weight of wax, tetraisopropylnaphthalene and rosin.
 7. A particulate slow release fertilizer composition which comprises a dispersion of a urea-paraffin wax adduct in a petroleum wax composition comprising a major amount of petroleum wax and a minor amount of tetraisopropylnaphthalene.
 8. Composition according to claim 7 wherein the amount of adduct is in the range of five to 99 parts and the amount of the wax-tetraisopropylnaphthalene composition is in the range of one to 40 parts.
 9. Composition according to claim 7 wherein the wax-tetraisopropylnaphthalene composition contains 5 to 40 percent of asphalt, based on the total weight.
 10. Composition according to claim 9 wherein the amount of adduct is in the range of 10 to 90 parts and the amount of the wax-tetraisopropylnaphthalene is in the range of 10 to 40 parts.
 11. A slow release fertilizer of improved resistance to water comprising a dispersion of solid urea in tetraisopropylnaphthalene, said fertilizer being characterized in that substantially all the particles of said solid urea are surrounded by and encased in tetraisopropylnaphthalene.
 12. A slow release fertilizer of improved resistance to water comprising a dispersion of solid urea in a solid composition comprising a major amount of tetraisopropylnaphthalene and a minor amount of wood rosin selected from the group consisting of (1) polymerized wood rosin, (2) hydrogenated wood rosin, (3) mono and polyhydric alcohol esters of polymerized, hydrogenated, and unmodified wood rosin, and (4) polyvalent metal salts of polymerized, hydrogenated, and unmodified wood rosin, each of (1), (2), (3), and (4) being partially oxidized to an extent equivalent to oxidation at 140* F. for a period of 1 to 8 days, said partial oxidation being sufficient to result in a decreased rate of leaching when said composition is contacted with water said fertilizer being characterized in that substantially all the particles of said solid urea are surrounded by and encased in said solid composition.
 13. Composition according to claim 12 wherein the amount of urea is five to 80 parts, the total amount of tetraisopropylnaphthalene and rosin is 15 to 49 parts, and the amount of rosin is 2 to 20 percent based on the total weight of tetraisopropylnaphthalene and rosin.
 14. Composition according to claim 12 having a minor amount of asphalt dissolved therein.
 15. A particulate slow release fertilizer composition which comprises a dispersion of a urea-paraffin wax adduct in tetraisopropylnaphthalene.
 16. Composition according to claim 15 wherein the amount of adduct is in the range of five to 99 parts and the amount of the tetraisopropylnaphthalene is in the range of one to 40 parts.
 17. Composition according to claim 15 wherein the tetraisopropylnaphthalene contains 5 to 40 percent asphalt based on the total weight of the asphalt and tetraisopropylnaPhthalene.
 18. Composition according to claim 17 wherein the amount of adduct is in the range of 10 to 90 parts and the amount of the tetraisopropylnaphthalene and asphalt is in the range of 10 to 40 parts. 